US20160051970A1 - Catalyst For Producing Methacrylic Acid And Method For Producing The Same, And Method For Producing Methacrylic Acid - Google Patents

Catalyst For Producing Methacrylic Acid And Method For Producing The Same, And Method For Producing Methacrylic Acid Download PDF

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US20160051970A1
US20160051970A1 US14/779,181 US201414779181A US2016051970A1 US 20160051970 A1 US20160051970 A1 US 20160051970A1 US 201414779181 A US201414779181 A US 201414779181A US 2016051970 A1 US2016051970 A1 US 2016051970A1
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liquid
catalyst
producing
methacrylic acid
aqueous solution
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Hideomi Sakai
Yosuke Konno
Tomoyuki Ejiri
Eiji Nishimura
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Assigned to NIPPON KAYAKU KABUSHIKI KAISHA reassignment NIPPON KAYAKU KABUSHIKI KAISHA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: EJIRI, Tomoyuki, KONNO, YOSUKE, NISHIMURA, EIJI, SAKAI, HIDEOMI
Publication of US20160051970A1 publication Critical patent/US20160051970A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation

Definitions

  • the present invention relates to a catalyst capable of stably producing a catalyst for producing methacrylic acid by subjecting methacrolein, isobutyl aldehyde or isobutyric acid to vapor phase catalytic oxidation without impairing a catalytic performance and a method for producing the same.
  • the invention also relates to a method for producing methacrylic acid using the catalyst.
  • a large number of catalysts have been proposed as a catalyst which is used for producing methacrylic acid by subjecting methacrolein, isobutyl aldehyde or isobutyric acid to vapor phase catalytic oxidation.
  • These catalysts are those containing molybdenum and phosphorus as main components and having a structure of a heteropoly acid and/or a salt thereof.
  • a large number of production methods of these catalysts have been similarly proposed.
  • Patent Document 1 discloses a method for preparing a catalyst for synthesizing acrolein or methacrolein by mixing two or more kinds of solutions or dispersion liquids containing catalytic components within a short period of time as far as possible, spray drying the resulting mixture immediately thereafter without being aged, and then calcining the resulting dry product.
  • Patent Document 2 discloses that a solution or slurry (A liquid) containing molybdenum and phosphorus, a solution or slurry (B liquid) containing an alkali metal and/or an alkaline earth metal, and a solution or slurry (C liquid) containing an ammonium radical are used, in which the A liquid and the B liquid are mixed, and the C liquid is then mixed.
  • a liquid a solution or slurry
  • B liquid containing an alkali metal and/or an alkaline earth metal
  • C liquid solution or slurry
  • it is preferable that the B liquid does not contain molybdenum or phosphorus.
  • Patent Document 3 discloses a method for preparing a heteropoly acid-based catalyst through two stages including obtaining a heteropoly acid containing at least molybdenum, phosphorus and cesium and then adding a catalyst raw material containing at least molybdenum and phosphorus but not containing cesium to the resulting heteropoly acid salt.
  • Patent Document 1 relates to a preparation method in which not only mixing is performed in a short time, but immediately thereafter, spray drying is performed, there is a concern about the method of stably producing a catalyst.
  • Patent Document 2 the mixing method of a preparation liquid is clearly elucidated.
  • the B liquid contains molybdenum or phosphorus
  • a more improvement is required in the yield of methacrylic acid.
  • Patent Document 3 the mixing method of a preparation liquid is clearly elucidated.
  • the mixture goes through a drying step, the heteropoly acid raw material is again added, followed by heating. Accordingly, this method is not economical.
  • the catalysts obtained in the manners as in Patent Documents 1 to 3 are not satisfactory yet in the reaction results, and hence, it is the present situation that more improvements are desired on the occasion of use as an industrial catalyst.
  • the invention is aimed to provide a catalyst for producing methacrylic acid in high yield and high selectivity by subjecting methacrolein, isobutyl aldehyde or isobutyric acid to vapor phase catalytic oxidation and a method for producing the same.
  • the present inventors have found that in a heteropoly acid neutralized salt compound containing, as essential active components, Mo, V, P, Cs, NH 4 and Cu, a catalyst produced by a specified method has an extremely high catalytic performance, leading to accomplishment of the invention.
  • the invention is concerned with the following.
  • Mo molybdenum
  • V vanadium
  • P phosphorus
  • (NH 4 ) represents an ammonium group
  • Cs cesium
  • Cu copper
  • X represents at least one element selected from the group consisting of Sb, As, Ag, Mg, Zn, Al, B, Ge, Sn, Pb, Ti, Zr, Cr, Re, Bi, W, Fe, Co, Ni, Ce and Th
  • O represents oxygen
  • a to g represent atomic ratios of the respective elements; a is satisfied with (0.1 ⁇ a ⁇ 6.0); b is satisfied with (0.5 ⁇ b ⁇ 6.0); c is satisfied with (0.1 ⁇ c ⁇ 10.0); d is satisfied with (0.1 ⁇ d ⁇ 3.0); e is satisfied with (0.1 ⁇ e ⁇ 3); f is satisfied with (0 ⁇ f ⁇ 3); and g is a numerical value determined according to oxidation states and atomic ratios of the respective elements other than O,
  • a liquid a heteropoly acid aqueous solution or heteropoly acid aqueous dispersion
  • B liquid a slurry liquid
  • C liquid a slurry liquid
  • a temperature of the aqueous solution or aqueous dispersion containing the A liquid and the cesium compound is from 0 to 35° C.
  • a catalyst for producing methacrylic acid which is obtained by the method as described in any one of (1) to (4) above.
  • a method for producing methacrylic acid comprising:
  • FIG. 1 is a graph in which an electric conductivity and a pH value of a mixed liquid in the step (b) of each of Examples 1 and 2 are shown on a Y axis, and a time is shown in terms of a minute unit on an X axis.
  • a solid line expresses the electric conductivity, and a dotted line expresses the pH value.
  • the catalyst for producing methacrylic acid which can be produced by the production method of the invention is one to be used on the occasion of subjecting methacrolein to vapor phase catalytic oxidation with molecular oxygen to produce methacrylic acid and has a composition represented by the following general formula (1).
  • Mo represents molybdenum
  • V represents vanadium
  • P represents phosphorus
  • (NH 4 ) represents an ammonium group
  • Cs represents cesium
  • Cu represents copper
  • X represents at least one element selected from the group consisting of Sb, As, Ag, Mg, Zn, Al, B, Ge, Sn, Pb, Ti, Zr, Cr, Re, Bi, W, Fe, Co, Ni, Ce and Th
  • O represents oxygen
  • a to g represent atomic ratios of the respective elements; a is satisfied with (0.1 ⁇ a ⁇ 6.0); b is satisfied with (0.5 ⁇ b ⁇ 6.0); c is satisfied with (0.1 ⁇ c ⁇ 10.0); d is satisfied with (0.1 ⁇ d ⁇ 3.0); e is satisfied with (0.1 ⁇ e ⁇ 3); f is satisfied with (0 ⁇ f ⁇ 3); and g is a numerical value determined according to the oxidation states and atomic ratios of the respective elements other than O.
  • the X component is preferably at least one element selected from the group consisting of Sb and As.
  • active component-containing compound which is used for the preparation of a catalyst when in addition to molybdenum, phosphorus and vanadium, each of which is an essential active component element in the step (a), essential active component elements in the step (d′) and arbitrary active component elements in the step (d′′) are exemplified, examples thereof include chlorides, sulfates, nitrates, oxides and acetates of the active component elements.
  • the compound include nitrates such as cobalt nitrate; acetates such as copper acetate; oxides such as molybdenum oxide, vanadium pentoxide, copper oxide, antimony trioxide, cerium oxide, zinc oxide, and germanium oxide; and acids (or salts thereof) such as orthophosphoric acid, phosphoric acid, boric acid, aluminum phosphate, and 12-tungstophosphoric acid.
  • nitrates such as cobalt nitrate
  • acetates such as copper acetate
  • oxides such as molybdenum oxide, vanadium pentoxide, copper oxide, antimony trioxide, cerium oxide, zinc oxide, and germanium oxide
  • acids (or salts thereof) such as orthophosphoric acid, phosphoric acid, boric acid, aluminum phosphate, and 12-tungstophosphoric acid.
  • the molybdenum oxide which is used for the production can be properly used in an average particle diameter ranging from 0.5 ⁇ m to 100 ⁇ m.
  • the slurry liquid can be obtained by uniformly mixing each active component-containing compound with water.
  • the amount of water used in the slurry liquid is not particularly limited so long as the whole of the compound used can be completely dissolved, or the compound used can be uniformly mixed. Taking a drying method or a drying condition into consideration, the amount of water used may be properly determined. In general, the amount of water is from about 200 to 2,000 parts by mass based on 100 parts by mass of a total mass of the compound for the preparation of slurry. Though the amount of water may be large, when it is excessive, there is often brought such a disadvantage that the energy costs of the drying step become high, or drying may not be completely achieved.
  • a temperature on the occasion of preparing a slurry liquid it is preferable to perform heating to a temperature at which the compound containing molybdenum, phosphorus and vanadium and optionally, other active component element can be thoroughly dissolved.
  • cesium compound which is added though any cesium compound may be used, cesium hydroxide or a weak acid salt such as cesium acetate and cesium carbonate is more preferable.
  • the electric conductivity may be measured by either an AC two-electrode method or an electromagnetic induction method.
  • the slurry liquid in the vicinity of a point of neutralization frequently becomes low in conductivity, it is preferable to measure the electric conductivity by an AC two-electrode method.
  • a conductivity meter manufactured by DKK-TOA Corporation is preferable as a measuring instrument, it should not be construed that the measuring instrument is limited thereto.
  • a part of the A liquid is mixed with an aqueous solution or aqueous dispersion of the cesium compound.
  • the part of the A liquid in the step (b) is determined by the atomic ratio d of the cesium to be added, it is added in an amount accounting for from 5 to 20% by weight, and preferably from 10 to 15% by weight in terms of a liquid amount relative to the whole of the A liquid.
  • the step (b) it is preferable to perform mixing in a ratio such that the electric conductivity of the mixture (B liquid) of a part of the A liquid and an aqueous solution or aqueous dispersion of the cesium compound lies in a point neutralization. For this reason, it is preferable that the amount of the heteropoly acid which is contained in the A liquid falls within the range that is a stoichiometric amount in the heterocyclic acid relative to the atomic ratio d of cesium.
  • a temperature of the A liquid is generally in the range of from about 0 to 35° C., and preferably from about 0 to 30° C. In that case, the resulting catalyst tends to become high in activity.
  • the C liquid obtained in the step (c) is mixed with an ammonium compound to obtain a slurry liquid.
  • the ammonium compound which is used in the step (d) is preferably ammonium acetate or ammonium hydroxide.
  • the addition step is not particularly limited, and the component or components may be properly added on the way or after completion of the steps (a) to (d).
  • the shape of a stirring blade of a stirrer which is used on the occasion of adding the essential active components is not particularly limited, and an arbitrary stirring blade such as a propeller blade, a turbine blade, a paddle blade, a pitched paddle blade, a screw blade, an anchor blade, a ribbon blade, and a large-sized lattice blade can be used in a single stage or two or more stages of the same blade or a combination of different kinds of blades in the vertical direction.
  • a baffle turning blade
  • the slurry liquid which has gone through the step (d) or the step (d′) after the step (d) is dried to obtain a catalytically active component solid.
  • the drying method in the step (e) is not particularly limited so long as the slurry liquid can be completely dried, examples thereof include drum drying, freeze drying, spray drying, and evaporation to dryness.
  • spray drying is preferable in the invention because the slurry liquid can be dried into a powder or granule within a short period of time.
  • a drying temperature of the spray drying varies depending upon the concentration or liquid feed rate of the slurry liquid, or the like, it is approximately from 70 to 150° C. in terms of a temperature at an outlet of a drying machine.
  • it is preferable to perform the drying such that an average particle diameter of the catalytically active component solid obtained on this occasion is from 10 to 700 ⁇ m.
  • the catalytically active component solid obtained in the above-described step (e) is molded.
  • the molding method in the step (f) is not particularly limited.
  • the catalytically active component solid for oxidation reaction in order to decrease a pressure loss of the reaction gas, the catalytically active component solid is molded in a columnar, tablet-like, ring-like or spherical form, or the like.
  • a rolling granulation method as described below is preferable for this coating step.
  • This method is, for example, a method in which in an apparatus having a flat or concave and convex disc in the bottom of a fixed container, the disc is rotated at a high speed, thereby vigorously agitating the carrier in the container by repeating rotation movement and revolution movement, and a binder and a coating mixture prepared by adding the catalytically active component solid and optionally, other additive such as a molding assistance and a strength improvement are coated on the carrier.
  • a method such as (1) a method of previously mixing the binder with the coating mixture; (2) a method of adding the binder simultaneously with the addition of the coating mixture in the fixed container; (3) a method of adding the coating mixture in the fixed container and then adding the binder; (4) a method of adding the binder before adding the coating mixture in the fixed container; and (5) a method of dividing each of the coating mixture and the binder and adding the whole by properly combining the methods (2) to (4) can be adopted.
  • the binder is preferably water, or at least one member selected from the group consisting of organic compounds having a boiling point of not higher than 150° C. at one atmosphere or lower, or an aqueous solution thereof.
  • the binder other than water examples include alcohols such as methanol, ethanol, propanols, and butanols, and preferably alcohols having from 1 to 4 carbon atoms; ethers such as ethyl ether, butyl ether, and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; and aqueous solutions thereof.
  • alcohols such as methanol, ethanol, propanols, and butanols, and preferably alcohols having from 1 to 4 carbon atoms
  • ethers such as ethyl ether, butyl ether, and dioxane
  • esters such as ethyl acetate and butyl acetate
  • ketones such as acetone and methyl ethyl ketone
  • aqueous solutions thereof examples of the binder other than water.
  • ethanol is preferable.
  • a ratio of ethanol to water is from 9.9/0.1 to 0.1/9.9 (mass ratio), and it is preferable to mix ethanol with water in a ratio of 9/1 to 1/9 (mass ratio).
  • the amount of such a binder used is generally from 2 to 60 parts by mass, and preferably from 10 to 50 parts by mass based on 100 parts by mass of the coating mixture.
  • the catalytic active component solid is calcined at from about 250° C. to 350° C., followed by molding, there may be the case where the mechanical strength or catalytic performance is enhanced, and such is preferable.
  • the carrier in the above-described coating include spherical carries having a diameter of from 1 to 15 mm, and preferably from 2.5 to 10 mm, such as silicon carbide, alumina, silica alumina, mullite, and Alundum.
  • a carrier one having a porosity of from 10 to 70% is generally used.
  • the carrier is used such that a ratio of the coating mixture to the total of the coating mixture and the carrier is generally from 10 to 75% by mass, and preferably from 15 to 60% by mass. In the case where the proportion of the coating mixture is too large, though the reactive activity of the coated catalyst is large, the mechanical strength tends to become small.
  • examples of the molding assistant which is used as the need arises include a silica gel, diatomaceous earth, and an alumina powder.
  • the amount of the molding assistant used is generally from 1 to 60 parts by mass based on 100 parts by mass of the catalytically active component solid.
  • an inorganic fiber for example, a ceramic fiber, a whisker, etc.
  • a strength improver as the need arises is useful for enhancing the mechanical strength of the catalyst.
  • a glass fiber is preferable.
  • the amount of such a fiber used is generally from 1 to 30 parts by mass based on 100 parts by mass of the catalytically active component solid.
  • the coated catalyst obtained in the step (f) can be directly subjected as a catalyst to a catalytic vapor phase oxidation reaction.
  • a calcination temperature is generally from 100° C. to 450° C., preferably from 250° C. to 420° C., more preferably 250° C. or higher and lower than 400° C., and still more preferably 300° C. or higher and lower than 400° C.
  • a calcination time is from 1 to 20 hours.
  • the calcination is generally performed in an air atmosphere, it may also be performed in an inert gas atmosphere of nitrogen, etc., or in a reductive gas atmosphere of ethanol, etc. After the calcination in an inert gas or reductive gas atmosphere, the calcination may be further performed in an air atmosphere.
  • a proportion of the active component to the whole of the thus obtained coated catalyst is from 10 to 60% by mass.
  • catalyst of the invention is used for the production of methacrylic acid by means of vapor phase catalytic oxidation of methacrolein, isobutyl aldehyde or isobutyric acid.
  • the vapor phase catalytic reaction with methacrolein that is the most preferable raw material for the use of the catalyst of the invention is hereunder described.
  • Molecular oxygen or a molecular oxygen-containing gas is used for the vapor phase catalytic oxidation reaction.
  • a proportion of the molecular oxygen used to methacrolein is preferably in the range of from 0.5 to 20, and especially preferably in the range of from 1 to 10 in terms of a molar ratio.
  • the raw material gas may contain, in addition oxygen and optionally, water (generally contained as water vapor), a gas which is inert against the reaction, such as nitrogen, carbon dioxide, and a saturated hydrocarbon.
  • a gas obtained by oxidizing isobutylene, tertiary butanol, and methyl tertiary butyl ether may be fed as it is.
  • a reaction temperature in the vapor phase catalytic oxidation reaction is generally from 200 to 400° C., and from 260 to 360° C., and the amount of the raw material gas fed is generally from 100 to 6,000 hr ⁇ 1 , and preferably from 300 to 3,000 hr ⁇ 1 in terms of a space velocity.
  • a pressure close to atmospheric pressure is generally suitable.
  • the B liquid was added to the remainder of the A liquid, to which was then gradually added 196.86 g of a 50.0% by mass ammonium acetate aqueous solution while stirring, and the contents were aged at 0° C. to 30° C. for one hour.
  • 22.18 g of cupric acetate was further added to the resulting slurry, and the contents were stirred and mixed at 0 to 30° C. until they were completely dissolved.
  • this slurry was spray dried to obtain a catalytically active component solid.
  • a composition of the catalytically active component solid as determined from the amounts of the raw materials charged is as follows.
  • a coated catalyst was prepared by the same method as that in Example 1, except that in Example 1, 661.32 g of the 9.1% by mass cesium hydroxide aqueous solution was changed to 417.07 g of a 9.1% by mass cesium nitrate aqueous solution, and then subjected to the catalytic oxidation reaction of methacrolein.
  • changes of the electric conductivity and pH value (Y axis) with time (X axis) of the mixed liquid obtained by adding the cesium nitrate aqueous solution to the A liquid are shown in FIG. 1 .
  • a coated catalyst was prepared by the same method as that in Example 1, except that in Example 1, 15.51 g of 30% by mass hydrogen peroxide water was added before adding cesium hydroxide, and then subjected to the catalytic oxidation reaction of methacrolein.
  • Example 1 After putting the B liquid, 13.15 g of 60% by mass arsenic acid was gradually added, and the contents were aged at 0° C. to 30° C. for one hour. Then, 196.86 g of a 50.0% by mass ammonium acetate aqueous solution was gradually added. Thereafter, a coated catalyst was prepared by the same method as that in Example 1 and then subjected to the catalytic oxidation reaction of methacrolein.
  • a coated catalyst was prepared by the same method as that in Example 1, except that in Example 1, after adding Cs, an ammonium acetate aqueous solution was added in a state where the electric conductivity was not neutralized, specifically immediately after completion of the addition of the cesium hydroxide aqueous solution, and then subjected to the catalytic oxidation reaction of methacrolein.
  • a coated catalyst was prepared by the same method as that in Example 1, except that in Example 1, after adding Cs, an ammonium acetate aqueous solution was added in a state where the electric conductivity was not neutralized, specifically 0.5 hours after completion of the addition of the cesium hydroxide aqueous solution, and then subjected to the catalytic oxidation reaction of methacrolein.
  • a coated catalyst was prepared by the same method as that in Example 1 and then subjected to the catalytic oxidation reaction of methacrolein.
  • a catalyst for producing methacrylic acid in high yield and high selectivity by subjecting methacrolein, isobutyl aldehyde or isobutyric acid to vapor phase catalytic oxidation and a method for producing the same can be provided.

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US14/779,181 2013-03-28 2014-03-24 Catalyst For Producing Methacrylic Acid And Method For Producing The Same, And Method For Producing Methacrylic Acid Abandoned US20160051970A1 (en)

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JP2013069908 2013-03-28
JP2013-069908 2013-03-28
PCT/JP2014/057990 WO2014157040A1 (fr) 2013-03-28 2014-03-24 Catalyseur pour la production d'acide méthacrylique, son procédé de production et procédé de production d'acide méthacrylique

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US (1) US20160051970A1 (fr)
EP (1) EP2979757A4 (fr)
JP (1) JP6387341B2 (fr)
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CN (1) CN105121011A (fr)
TW (1) TW201501793A (fr)
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WO2018217962A1 (fr) 2017-05-25 2018-11-29 Rohm And Haas Company Procédé de préparation de méthacrylaldéhyde

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CN105289675A (zh) * 2015-10-21 2016-02-03 中国科学院过程工程研究所 一种用于异丁烯醛氧化制异丁烯酸纳米杂多酸催化剂
CN105797772B (zh) * 2016-04-25 2018-06-05 宁波工程学院 一种掺杂杂多酸催化剂及在可见光下光解水制氢气的方法
CN105833908B (zh) * 2016-04-26 2018-06-01 宁波工程学院 一种掺杂杂多酸催化剂及在可见光下光解水制氢气的方法
CN109731592B (zh) * 2019-01-16 2020-12-01 中国科学院过程工程研究所 甲基丙烯醛选择性氧化制甲基丙烯酸的催化剂及其制备方法和用途
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CN114425377B (zh) * 2020-09-24 2023-10-10 中国石油化工股份有限公司 一种邻苯二甲醛催化剂、制备方法及应用

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2847150B2 (ja) 1990-11-14 1999-01-13 三井化学株式会社 アクロレイン又はメタクロレインの製造方法
JPH05177141A (ja) 1991-12-27 1993-07-20 Tosoh Corp メタクリル酸の製造法
JPH0924277A (ja) * 1995-07-14 1997-01-28 Sumitomo Chem Co Ltd メタクリル酸製造用触媒及びメタクリル酸の製造方法
JP4017864B2 (ja) * 2001-12-27 2007-12-05 三菱レイヨン株式会社 メタクリル酸製造用触媒の製造方法、および、メタクリル酸の製造方法
JP2005066476A (ja) * 2003-08-25 2005-03-17 Mitsubishi Rayon Co Ltd メタクリル酸製造用触媒の製造方法、この方法により製造される触媒、およびメタクリル酸の製造方法
JP4925415B2 (ja) 2006-04-19 2012-04-25 三菱レイヨン株式会社 メタクリル酸製造用触媒の製造方法
JP5362370B2 (ja) * 2009-01-14 2013-12-11 三菱レイヨン株式会社 メタクリル酸合成用触媒の製造方法
JP4900449B2 (ja) * 2009-10-30 2012-03-21 住友化学株式会社 メタクリル酸製造用触媒の製造方法及びメタクリル酸の製造方法
JP2011152543A (ja) * 2011-04-28 2011-08-11 Nippon Kayaku Co Ltd メタクリル酸製造用触媒の製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018217962A1 (fr) 2017-05-25 2018-11-29 Rohm And Haas Company Procédé de préparation de méthacrylaldéhyde
WO2018217961A1 (fr) 2017-05-25 2018-11-29 Rohm And Haas Company Procédé de préparation de méthacroléine
US10723685B2 (en) 2017-05-25 2020-07-28 Rohm And Haas Company Process for preparing methacrolein
US10836699B2 (en) 2017-05-25 2020-11-17 Rohm And Haas Company Process for preparing methacrolein

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